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Chlorophyll-quinone photochemistry in liposomes: mechanisms of radical formation and decay

Technical Report ·
DOI:https://doi.org/10.2172/6569077· OSTI ID:6569077
Laser flash photolysis has been used to investigate the mechanism of formation and decay of the radical species generated by light induced electron transfer from chlorophyll a triplet to quinone in egg phosphatidyl choline bilayer vesicles. Chlorophyll triplet quenching by quinone is controlled by diffusion occurring within the bilayer membrane and reflects bilayer viscosity. Radical formation via separation of the intermediate ion pair is also inhibited by increased bilayer viscosity. Cooperativity is observed in this process due to an enhancement of radical separation by electron transfer from semiquinone anion radical to a neighboring quinone molecule. Two modes of radical decay are observed, a rapid recombination occurring within the bilayer and a much slower recombination occurring across the bilayer. The slow decay is only observed with quinones which are not tightly anchored into the bilayer, and is probably the result of electron transfer from semiquinone anion radical formed within the bilayer to a quinone molecule residing at the bilayer-water interface. With benzoquinone, approximately 60% of the radical decay occurs via the slow mode. Triplet to radical conversion efficiencies in the bilayer systems are comparable to those obtained in fluid solution (approx. 60%). However, radical recombination, at least for the slow decay mechanism, is considerably retarded.
Research Organization:
Arizona Univ., Tucson (USA)
OSTI ID:
6569077
Report Number(s):
DOE/ER/04927-T3
Country of Publication:
United States
Language:
English